Water repellence fixative treatment



Patented June 9, 1953 WATER REPELLENCE. FIXATIVE' TREATMENT 1 Stephen F;Urban, Kenmore, and Warren. B. Blumenthal, Niagara Falls, N. Y.,assignors to National LeadCompany, New York, N. Y., a corporationof NewJersey No Drawing. Application December 24, 1948, Serial No. 67,254

7 Claims. (01. 117-454) The present invention relates to the treatmentof fibrous materials such. as: textile fabrics and fibrous cellulosicsheet material, for instance, paper and cardboard, in order to rendersuch fibrous material resistant to wetting and to penetration by Water.More particularly, the invention relates to a method for inducing waterrepellence in the fibrous material treated by the employment of aspecific water soluble, alkaline zirconium compound, i. e., ammoniumdicarbonato zirconylate, and the fixation of the zirconium compound, ora decomposition product thereof, upon the material so treated, wherebythe effects of the water repellent treatment will endure throughconditions which normally clestroy it, either partially or completely.In general, laundering and dry cleaning are examples of processes whichdestroy Water repellence effects. v I p So-called water repellenceprocesses have little or no effect upon the normal porosity, texture,appearance and other perceptible qualities of the fabric or paper, asidefrom its resistance to wetting and penetration by water, and in thisrespect differ from Water-proofing processes wherein the fibers of thematerial are coated and the pores of the material are closed by thewater-proofing composition. Fibrous materials having water re pellentsurfaces, therefore, in general, merely resist wetting of theconstituent fibers and the socalled water repellence does not preventpenetration of water into the pores under hydrostatic head.Water-proofing operations are generally more permanent than waterrepellent operations,

since the materials employed in the latter process are relatively morereadily removed by ordinary laundering and dry cleaning operations.

It is an object of the present invention to provide a method of treatingfibrous materials to obtain water repellence therein and more per-.manently to fix the water repellence material upon the fibers of theproduct so treated.

treating material with elimination of the excess solution.

The zirconium compound adheres to the fibrous material being treated andserves to bind to the surface thereof a film of fatty and/or waxy 2material normally incorporated in the. solution of the water repellencecompound. This film then comprises the hydrophobic exterior of thefibers and is responsible for the water repellent quality. Thehydrophobic film thus formed on the material to which water repellentproperties are to be imparted is then fixed or anchored on the fibers ofthat material by a subsequent treatment with a water soluble salt of apolyvalent metal selected from the groups 111', IV and VIII of theperiodic system, or a mixture of such salts. The anion of the salt ofthe polyvalent metal appears when used alone to furnish little or nofixative action, this property being induced only when it is used inconjunction with the polyvalent cation. Although the fixative action isa general function of the polyvalent cations of the metals of the statedgroups, it will generally be found advantageous to employ salts of suchcat.- ions which produce colorless aqueous solutions as, for instance,zirconium, tin, aluminum, and others. Immediately, after th action ofthe fixative salt upon the fibrous material which has been treated withthe soluble double ammonium zirconium carbonate, the material may berinsed without dislodging or destroying the water repeilence effect ofthe hydrophobic film. After rinsing, the fabric or fiber sheet is driedgenerally at an elevated temperature and will be found to possess verystrong and sustained water repellence. For instance, fabrics so treatedwill exhibit a spray rating of to and paper will shed a spray of water.It will be noted that-water dropped upon horizontally placed'papersheets so treated will form roundedglobules, whereas on untreated paper.the drops flatten out and wet the paper. Cloth rendered water repellentwithout the application of the fixative will withstand one to twolaunderingswith Ivory soap, without losing its water repellence, Whilesimilar cloth treated with the fixative can withstand four to eight suchlaunderings. Furthermore, a single dry cleaning normally destroys thewater repellent quality when no fixative is employed. How- .ever,.similar cloths made water repellent by including the fixative treatmentof the present invention have been found to withstand sixdry cleanings.

The following examples are given merely by way of illustration and arenot to be deemed as limiting the scope of the invention but as merelyillustrative of it as there will obviously be many variations of time,temperature and composition of bath, suitable'for employment in order toobtain the results of the invention.

Example I Anaqueousso1ution of ammonium dicarbonato zirconylate,(NH4),2ZrO(C'O3)2, containing one- 'this bath for one minute, thenremoved and rolled free of excess liquid. The so treated paper was thenimmersed for two minutes in a solution containing 1.9 gm. of basiczirconyl chloride (Z1'2O3C12.6H2O) dissolved in 100 ml. of Water. Afterremoval from this solution, the material was rinsed thoroughly in waterand dried at 90 C. (194 F.). It was rendered highly water repellent bythis process.

A sample of cotton drill treated in the same fashion withstood eightlaunderings, while another sample withstood six dry cleaning operationsbefore losing its water repellence characteristics.

Example II Same as Example I except that 3.0 gm. of stannous chloridewas used in place of the basic zirconyl chloride.

Example III Same as Example I except that 2.5 gm. of ferrous sulfate wasused in place of the basic zirconyl chloride.

' Example IV A strip of paper of the type used for application theretoof sensitized photographic gelatin,

I and in which it is desired to produce hydrophobic characteristics, wasimmersed in an aqueous solution of the double ammonium zirconiumcarbonate, i. e. ammonium dicarbonato zirconylate, containing about 12.3gm. ZrO2, 13 gm. ammonium palrnitate, and 12.3 gm. dispersed wax. Afterimmersion for one minute at 40 0., the paper was removed, dipped inwater and then passed through rollers to remove excess of liquid.

The Water repellence ingredients of the bath Patent No. 2,457,853,granted January 4, 1949. It

will be understood that the usual fatty substances forming soa can beemployed herein, i. e.,'the soluble salts of oleic acid, palmitic acid,stearic acid and the like, and that if waxes be added to the bath, otherWaxes may be used in lieu of the paraffin wax employed in theillustrated examples,

The procedures of the present invention have particular application toimprove water repellence treatments of fibrous fabrics and to successfulwater repellence treatments of fibrous cellulosic sheets as, forinstance, paper sheets to be employed in the manufacture of sensitizedphotographic and print paper.

What is claimed is:

1. A process for inducing water repellance in cellulosic fibrousmaterials which comprises immersing the fibrous material in an aqueousbath containing ammonium dicarbonato. zirconylate 4 and a water solublesoap, and thereafter immersing said so treated material in an aqueoussolution containing a salt which yields a cation of a metal selectedfrom the group of metals of groups three, four and eight of Mendeleefisperiodic arrangement of the elements, then rinsing and dry ing thematerial.

2. Aprocess for inducing .water repellance in cellulosic fibrousmaterials which comprises immersing the fibrous material in an aqueousbath containing ammonium dicarbonato zirconylate and a water solublesoap, and thereafter immersing said material in an aqueous solutioncontaining a soluble zirconium salt wherein zirconium is a cation, thenrinsingand drying the material.

3. A process for inducing water repellance in cellulosic fibrousmaterials which comprises immersing the fibrous material in an aqueousbath containing ammonium dicarbonato zirconylate and a water solublesoap, and thereafter immersing said material in an aqueous solutioncontaining a soluble aluminum salt wherein aluminum is a cation, thenrinsing and drying the material.

4. A process for inducing water repellance in cellulosic fibrousmaterials which comprises immersing the fibrous material in an aqueous.bath containing ammonium dicarbonato zirconylate and a water solublesoap, and thereafter immersing said material in an aqueous solutioncontaining a soluble tin salt wherein tin is a cation, then rinsing anddrying the material.

5. A process for inducing'water repellance in paper which comprisesimmersing the paper in an aqueous water repellance bath containing awater soluble soap and a water soluble alkaline double ammoniumzirconium carbonate for a time suficient to saturate the paper with thesolution, thereafter immersing the so saturated paper in anaqueoussolution of zirconyl chloride to fix-the water repellance materials uponthe fibers of the paper, then rinsing and drying the paper.

6. A fibrous material having water repellance properties comprising abase of c'ellulosic fibrous material, a hydrophobic coating thereon ofthe reaction product of an aqueous solution of ammonium dicarbonatozirconylate and a water soluble soap and a fixative for said coatingcomprising a polyvalent metal cation selected from the group of metalsconsisting of groups three, four and eight of Mendeleefis periodicarrangement of the elements.

'7. A paper sheet having water repellance properties and having on thesurface thereof a hydrophobic coating of the reaction product of anaqueous solution of ammonium dicarbonato zirconylate and a water solublesoap and a fixative for said coating comprising a polyvalent metalcation selected from the group of metals consisting of groups three,four and eight of Mendeleeifs periodic arrangement ofthe elements.

STEPHEN F. URBAN. WARREN B. BLUMENTHAL.

References Cited in the file of this patent UNITED STATES PATENTS NumberName Date 1,799,949 Boughton' Apr. '7, 1931 2,165,265 Hubert et a1 July11, 1939 2,323,387 Edelstein July 6, 1943 2,361,830 Edelstein Oct. 31,1944 2,457,853 Van Mater Jan. 4, 1949

1. A PROCESS FOR INDUCING WATER REPELLANCE IN CELLULOSIC FIBROUSMATERIALS WHICH COMPRISES IMMERSING THE FIBROUS MATERIAL IN AN AQUEOUSBATH CONTAINING AMMONIUM DICARBONATO ZIRCONYLATE AND A WATER SOLUBLESOAP, AND THEREAFTER IMMERSING SAID SO TREATED MATERIAL IN AN AQUEOUSSOLUTION CONTAINING A SALT WHICH YIELDS A CATION OF A METAL SELECTEDFROM THE GROUP OF METALS OF GROUPS THREE, FOUR AND EIGHT OFMENDELEEFF''S PERIODIC ARRANGEMENT OF THE ELEMENTS, THEN RINSING ANDDRYING THE MATERIAL.